CN104114745A - Nanoporous layers for optical applications - Google Patents
Nanoporous layers for optical applications Download PDFInfo
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- CN104114745A CN104114745A CN201380008510.7A CN201380008510A CN104114745A CN 104114745 A CN104114745 A CN 104114745A CN 201380008510 A CN201380008510 A CN 201380008510A CN 104114745 A CN104114745 A CN 104114745A
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- silicon oxide
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- 229910001864 baryta Inorganic materials 0.000 description 1
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- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 229920002313 fluoropolymer Polymers 0.000 description 1
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- 238000010574 gas phase reaction Methods 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- FRDUMPXQKRIRMQ-UHFFFAOYSA-A octaaluminum;zirconium(4+);octachloride;icosahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4] FRDUMPXQKRIRMQ-UHFFFAOYSA-A 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920001279 poly(ester amides) Polymers 0.000 description 1
- 229920001691 poly(ether urethane) Polymers 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000002745 poly(ortho ester) Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- VGXPYLCBMMMTKL-UHFFFAOYSA-A tetraaluminum;zirconium(4+);tetrachloride;dodecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[Al+3].[Cl-].[Cl-].[Cl-].[Cl-].[Zr+4] VGXPYLCBMMMTKL-UHFFFAOYSA-A 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
- B05D1/305—Curtain coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Laminated Bodies (AREA)
- Optical Filters (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a layer structure comprising a substrate layer and a layer, which comprises a plurality of silicon oxide particles, wherein said silicon oxide particles have a positively charged surface (a PCS layer), which PCS layer is at least partially superimposed to the substrate layer and wherein the refractive index of the PCS layer is less than 1.2, a process for preparing the layer structure having a substrate and a PCS layer, a layer structure obtainable by the process, an optical device comprising the layer structure and the use of a PCS layer.
Description
The present invention relates to a kind of layer structure that comprises stratum basale and layer, described layer comprises many silicon oxide particles, wherein said silicon oxide particle has positively charged surface and (is called as below: PCS layer), described PCS layer is superimposed to described stratum basale at least in part, and the specific refractory power of wherein said PCS layer is less than 1.2; A kind of method for the manufacture of thering is the layer structure of substrate and PCS layer; A kind of layer structure that can obtain by described method; Comprise the described layer optics of structure and the purposes of PCS layer.
In multiple application, exist thin, smooth, the transparent and/or ever-increasing demand of diathermic wall.Outstanding example is photovoltaic applications, wherein needs film to have the two or more combination in afore-mentioned characteristics.In addition, exist on the one hand miniaturization always and improve on the other hand the trend of efficiency.Therefore,, for exploitation is thinner, more smooth, more transparent and/or the better layer of heat insulating ability, working hard always.
Especially in photovoltaic applications, constantly find and there is low-refraction (n
d) material.Use these materials to manufacture multilayer film and coating, so that the layer of the high transmission of the light providing passing through, low reflection and low absorption to be provided.Turn to the material that can be used for manufacturing this type of layer, dense matter is that restriction is used, because most of transparent material, as glass and PMMA have the specific refractory power that is greater than 1.45.Only exist and there is the minority solid material to the specific refractory power in 1.45 scopes at 1.0 (air), for example, there is n
d 20=1.38 magnesium fluoride, Sodium Fluoride (n
d 20=1.32) and some organic fluoride-containing compounds, its specific refractory power is in the scope of 1.34-1.38.
A kind of approach is to use compound as aluminum oxide (n
d 20=1.76), boehmite (n
d 20=1.65) or amorphous silica (n
d 20=1.46) manufacture porous material, thereby be less than n
d 20=1.4 specific refractory power.The example of these type materials is usually said aerogels, at silicon dioxide structure, comprises the mesoporous silica in the hole (air) that is greater than 90%.By adjustment hole volume and size, the mark of air in silicon dioxide structure, can obtain the material with any specific refractory power between 1.02 to 1.46.Yet aerogel is to water sensitive and deteriorated under wet condition.This makes manufacturing process even more complicated, because aerogel is normally manufactured in sol-gel method.Therefore, the defect of aerogel structure is general.Another shortcoming of aerogel method is to use original quanmethyl silicate, and it is poisonous and is reluctant in addition.Set forth alternative manufacture method, but these methods imply other shortcomings, as to the restriction of obtainable specific refractory power (BASF method) or low transformation efficiency.From industrial viewpoint, other shortcoming is, can not Direct precipitation aerogel in many substrates, because substrate can not accepted to obtain the required drying conditions of aerogel by sol-gel method.By aerogel on printed circuit board (PCB) or for example, for the production of multilayered structure (, luminescent device or leaded light device) in, this is special shortcoming.All these hints have limited the use of aerogel, and in industrial production, are obvious cost factors.Finally, large-scale manufacture is very limited.
The approach that another kind obtains the layer of low-refraction is sol-gel coating method, and wherein, by colloidal sol, for example silicon sol (negatively charged ion) or aluminium colloidal sol (positively charged), be coated in substrate.During liquid phase evaporation, by the gathering of residual particles, form afterwards the precursor of porous layer.Finally, pyrolysis removes the organic residue of Guinier-Preston zone and is conducive to further polycondensation, and therefore supports the mechanical stability of resulting porous layer.During solvent evaporation, there are some and shrink in layer, and this causes crackle to form.During pyrolysis, because act on the thermal stresses of layer, promote the further formation of crackle.Yet when light passes through this layer, these crackles cause the scattering phenomenon in layer.
In addition normally fragility and insufficient substrate, for example plastics sheet of being attached to of inorganic layer.Yet current optics and electricity device need to be flexible at least to a certain extent conventionally.Lastingly bonding is necessary in addition.The common mode addressing these problems is to use adhesion promotor.Yet adhesion promotor is organic, dense material, it has the specific refractory power than porous floor height.In addition, adhesion promotor not only can provide bonding at layer-substrate interface place, but also can be filling porous the hole of layer.Like this, the specific refractory power of layer structure will increase.
Therefore, in ever-increasing demand exploitation to the extra layer of low-refraction, high-transmission rate, antiradar reflectivity and low-yield specific absorption.In addition, need to improve the method for the manufacture of these materials and these layers.Especially, observe carrying out than the lower cost of current technology the demand of manufacturing processed under large technical scale.In addition, seek more efficient photoconduction, light source and electrical insulator, and production cost reduces.
Therefore, the object of the invention is, the optics with low optical loss is provided.Another object of the present invention is to provide optics, and it is more efficient or sensitiveer, or either more efficiently but also sensitiveer.
Another object of the present invention is to provide and can be coated to by extensive coating technique the heat insulator of substrate.
Another object of the present invention is to provide the means for the simplified construction of optics, for example, by realizing the simplified construction of the assembly of optics.Consistent with it, another object of the present invention is to reduce the cost of manufacturing optics and optics element.
Another object is to provide for forming the means of thinner device or device element.
Another object of the present invention is to provide the means of the device of weather resistance, accuracy and the accuracy for forming with raising.
Another object of the present invention is to provide optics and/or finish paint, and it has the scratch resistance of raising.
Another object of the present invention is to provide the interface between air and dense matter, and wherein said interface display goes out seldom to not reflection.
Another object of the present invention is to provide the layer in the temperature range of 100 ℃ at the most with good thermal stability.
Another object of the present invention is provided for manufacturing the technology of porous silica layer and the goods with low-refraction, in described technology, reduces or even avoid the use of hazardous material.In this technology, should pay further effort to avoid volatile organic compounds (VOC).
Another object of the present invention is to provide porous silica layer, its be not fragility but flexible and fully adhere to its coated substrate.
Unexpectedly, have been found that at least one comprising in the layer solution above-mentioned purpose with positively charged surperficial silicon oxide particle.In addition, have been found that the manufacture method that has positively charged surperficial silicon oxide particle for these is acceptable on environment, and need to be easily to realize according to industry.In addition, the use of this type of layer contributes to the exploitation of thinner device and device element, because can reduce the quantity of parts in device.In the situation that two parts of needs are separated from each other two optical layers, present parts are just enough, and these two optical layers are separated by PCS layer of the present invention therein.This is also considered to manufacture and has a more aspect of more cheap, the more durable parts of high accuracy and accuracy degree.
Form the claim (independent claim of class, category-forming claim) theme provides at least one the contribution of settling mode in above object, thereby the dependent claims (dependent sub-claim) that forms the independent claim of class represents preferred aspect of the present invention, its theme is made equally to solving at least one the contribution in above-mentioned purpose.
A first aspect of the present invention is a kind of layer of structure, and described layer structure comprises
(a) stratum basale, is preferably transparent substrates layer; With
(b) PCS layer, described PCS layer is superimposed to described stratum basale at least in part,
Wherein said PCS layer comprises many silicon oxide particles,
Wherein said silicon oxide particle has positively charged surface,
The specific refractory power of wherein said PCS layer is less than 1.2, is preferably less than 1.17, is less than 1.15, or 1.19 to 1.01.
The following describes for determining the method for specific refractory power.
Term is transparent in characterizing such goods in the context of the present invention: the light that wavelength X is 350nm to 800nm can pass through described goods, thus the light quantity by described article or system be enter described goods light quantity at least 85%.
Term is opaque for characterizing such goods in the context of the present invention: the light that wavelength X is 350nm to 800nm can pass through described goods, thus the light quantity by described article or system be less than enter described goods light quantity 6%.
When the zeta-potential of article is greater than 0mV, for example the surface of silicon oxide particle is positively charged in surface to think goods.Zeta-potential can be determined according to the method for the following stated.
Layer representation according to the present invention comprises that two with the plural form on upper strata, and at least a portion in its middle level and at least a portion of at least one adjacent layers interconnect.
According to an aspect of the present invention, described stratum basale comprises at least one in following article: paper, resin coating paper, Japanese thin paper (japanese tissue paper), card board kai, metal, as aluminium, tinsel, base metallization, for example the polymkeric substance of depositing metal layers, glass and flexible glass be (for example: by Corning thereon, Inc., " gorilla glass (the Gorilla Glass) " that USA manufactures).
According to another aspect of the present invention, described stratum basale comprises at least one polymkeric substance.Many known polymkeric substance enter in those skilled in the art's consideration.Preferably, polymkeric substance is included in stratum basale.Preferably, polymkeric substance choosing is the group of following composition freely: cellulose ester is as cellulose triacetate, rhodia, cellulose propionate or acetic acid/cellulose butyrate, polyester is as polyethylene terephthalate or PEN, polymeric amide, polycarbonate, polyimide, polyolefine, polyvinyl acetal, polyethers, polyvinyl chloride, polyvinylidene difluoride (PVDF), polyvinyl sulfone, vinyl cyanide, divinyl, vinylbenzene, polycarbonate, polyetherimide, polyester ketone, poly-(methyl methacrylate), polyoxymethylene and polystyrene, or its two or more combination.
In addition, polymkeric substance is preferably selected from the group being comprised of following: aliphatic polyester is as polycaprolactone, poly-(beta-propiolactone), poly-(hydroxyalkanoate), poly-(butyric ester), poly-(oxyacetic acid), poly-(beta-malic acid), poly-(succsinic acid alkylene ester), poly-(succsinic acid butylidene ester), PLA, starch blend, poly-(para-dioxane), the cellulose acetate with low acylations degree, poly-(vinyl alcohol), polymeric amide, poly-(amino acid), false poly-(a-amino acid), poly-(α-aminoacidesters), copolyesters, copolyamide, poly-(esteramides), poly-(ester urea), poly-(iminocarbonic ester), polyanhydride, PEG, poly-(ortho ester), poly phosphazene, urethane, poly-(ester ammonia ester), poly-(ether urethane), poly-(ammonia ester urea), polystyrene, polyolefine is as polypropylene, aliphatic-aromatic copolyesters is as the copolyesters of polycaprolactone with poly-(ethylene glycol terephthalate), polycaprolactone and the copolyesters that gathers (mutual-phenenyl two acid bromide two alcohol ester), polycaprolactone and the copolyesters that gathers (ethylene isophthalate), the copolyesters of hexanodioic acid and terephthalic acid, BDO, the copolyesters of hexanodioic acid and terephthalic acid, or its combination of at least two kinds.
According to another aspect of the present invention, described stratum basale is the two or more matrix material comprising in aforementioned substrates layer material.
Preferably, stratum basale is transparent.Transparent substrates layer can mainly be obtained by above-mentioned polymkeric substance.Yet, must control manufacturing processed and there is appropriate configuration as the material of crystallite to obtain, the size of wherein said structure is less than 1/4th of the light wavelength passed through.If for example stratum basale is exposed to the light of the wavelength X in 350nm to 800nm scope, the structure existing in transparent layer should be less than 350/4nm=87.5nm.More preferably, the structure in transparent layer is less than 60nm or is less than 50nm or is less than 40nm.Conventionally, amorphous material meets aforementioned requirement.Thus, think that the size of described structure is the longest straight line that passes through described structure on upper 2 of syndeton surface.
According to another aspect of the present invention, described stratum basale can be opaque.Many known opaque materials enter in those skilled in the art's consideration.For the preferred material of opaque substrate, be those materials that photographic industry is known, for example barytage paper (baryta paper), polyolefin coating paper or with the polyester in space (as manufactured by Du-Pont Tejin films
).
In addition, layer structure according to the present invention comprises at least one PCS layer, and it is superimposed to stratum basale.In the context of the invention, term stack is used for describing the first article, PCS layer for example, and with respect to the second article, for example the second layer is as the relative position of stratum basale.Likely, can between the first article and the second article, arrange extra article, for example pearl or layer.Preferably, PCS layer is superimposed to stratum basale at least in part, for example account for layer structure area at least 30%, 50%, 70% or account at least 90%.
According to another preferred aspect of the present invention, PCS layer is connected with stratum basale.In the context of the invention, term is connected for describing following truth: two stack article for example two superimposed layers connect.Preferably, two stack article be connected to small part, with respect to the area of the stack of two article, for example, account at least 30%, 50%, 70% or account at least 90%.
Conventionally, many means and technology enter in those skilled in the art's consideration to be connected two layers, they be known and performance suitably.Preferably, two layers can pass through electrostatic interaction, chemical bonding, Van der Waals force or its combination of at least two kinds and are connected.According to another preferred aspect, before a layer being disposed on another layer, by tackiness agent being coated at least one surface of two layers, can further connect two layers.According to the preferred method of another kind, liquid phase can be coated on the first layer, by separated at least a portion liquid from described liquid phase, for example, by solvent and/or water are evaporated from dispersion liquid or solution, described liquid phase forms layer extra, preferred solid on the first layer.Layer structure optimization according to the present invention comprises a plurality of plural layers, and wherein at least a portion of one deck and at least a portion of at least one adjacent layers are connected.
At least one PCS layer comprises many silicon oxide particles.Two kinds of main methods are widely used in the silicon oxide particle of manufacturing small particle size.In first method, in wet processes, precipitate (silicon-dioxide of precipitation).In the second approach, gas-phase reaction produces required silicon oxide particle (pyrogenic silica).Conventionally by flame pyrolysis, for example, by the silicon tetrachloride that burns under the existence at hydrogen and oxygen, prepare this pyrogenic silica.The commerical prod of multiple pyrogenic silica is with from Evonik Industries AG, Essen, the trade(brand)name of Germany
provide.Another kind of commerical prod is
h-5, can be from Cabot Corporation, Billerica, and the U.S. obtains.
According to another aspect of the present invention, the median size of the silicon oxide particle existing in PCS layer is, preferably in liquid phase, determine, in 1 to 200nm scope, preferably in 10 to 200nm scope, preferably in 30 to 150nm scope, more preferably in 30 to 120nm scope, also more preferably in 30 to 90nm scope, more more preferably in 30 to 80nm scope, or in 35 to 75nm scope, most preferably in 40 to 70nm scope.If above-mentioned those silicon oxide particle is aggregate.The silicon oxide particle of these aforementioned dimensions scopes is commonly called " nano particle ".The median size d of this type of aggregate
50be defined as diameter, (aggregate) 50 quality % of sample have larger diameter, and other 50 quality % have less diameter.Can use multiple technologies, for example, use centrifugal settling particle size analyzer, measure the diameter of aggregate.
According to another aspect of the present invention, described layer structure forms a freely part for the optics of the group of following composition of choosing: luminescent device, photocon, optical transform device, optical recording device and electric insulation layer or two or more combination in them.
Many known optics that are selected from above-mentioned group enter in those skilled in the art's consideration.Preferred luminescent device choosing is the group of following composition freely: face plate illumination, plate lighting, floodlight, headlight, spot light lamp and electronic console.Preferred photocon choosing is the group of following composition freely: plane and on-plane surface photoconduction.Preferred optical transform device choosing is the group of following composition freely: convertor of colors and colour filter.Preferred optics is antireflection device and light diffuser part in addition.In addition the two or more system in, can the aforementioned optics of Selection and Constitute.In these, system is as preferred in indicating meter, photographic camera and projector.
According to another aspect of the present invention, the cumulative volume based on PCS layer separately, described PCS layer has within the scope of 55 to 80 volume %, the preferred pore volume within the scope of 60 to 75 volume %.Pore volume can be determined by the method for the following stated.
The BET specific surface area of the silicon oxide existing in PCS layer according to another aspect of the present invention, is at 20m
2/ g to 600m
2in the scope of/g, preferably at 50m
2/ g to 550m
2in the scope of/g, more preferably at 70m
2/ g to 500m
2in the scope of/g, also more preferably at 100m
2/ g to 400m
2in the scope of/g.
According to another aspect of the present invention, the silicon oxide particle existing in PCS layer has positively charged surface.When the zeta-potential of article is greater than 0mV, for example the surface of silicon oxide particle is positively charged in surface to think article.Preferably, the surface of applicable silicon oxide there is be greater than+20mV, the zeta-potential of be greater than+30mV or be greater than+40mV.Therefore, the preferred scope of zeta-potential is 0 to+100mV, 0 to+70mV, 0 to the+scope of 50mV, 20mV to 50mV, 25mV to 50mV, 30mV to 50mV, 35mV to 50mV or 35mV to 50mV.
According to another aspect of the present invention, the silicon oxide particle existing in PCS layer can also comprise freely at least one compound of the group of following composition of choosing: trivalent aluminum compound, tetravalence zirconium compounds, amido organosilicon hydride compounds, the reaction product of at least one trivalent aluminum compound and at least one amido organosilicon hydride compounds, the reaction product of at least one tetravalence zirconium compounds and at least one amido organosilicon hydride compounds, the reaction product of at least one trivalent aluminum compound and at least one tetravalence zirconium compounds and at least one amido organosilicon hydride compounds, and combination.
Preferably, at least on the surface of particle, carry out the modification of silicon oxide particle.Therefore the silicon oxide particle, existing in PCS layer at least comprises at least one aforesaid compound on particle surface.Another preferred aspect of the present invention relates to this modification, and it can carry out on particle, particle agglomerate or the surface of the two and in chamber.Therefore the silicon oxide particle, existing in PCS layer at least comprises at least one aforesaid compound on particle surface and at least some chambeies of particle.
Its surface is by processing and the silicon oxide particle of modification with Wickenol CPS 325, is preferably according to of the present invention, to have a positively charged surperficial silicon oxide particle.
By processing with zirconium compounds, the silicon oxide particle of modification is on its surface, preferably according to of the present invention, has a positively charged surperficial silicon oxide particle.
Its surface is by processing and the silicon oxide particle of modification with amino-organosilanes, is another kind ofly preferably according to of the present invention, to have a positively charged surperficial silicon oxide particle.
Has processed by the compound with trivalent aluminum compound (as Wickenol CPS 325) or tetravalence zirconium (as zirconyl chloride, zirconium carbonate, zirconium acetate or zirconium lactate) or reaction product that the two preferably reacts with at least one amino-organosilanes on its surface and the silicon oxide particle of modification is, another kind of preferably have a positively charged surperficial silicon oxide particle according to of the present invention.
By processing with aluminum-zirconium hydration complex compound (as three aluminum chlorhydrate's zirconiums, tetrachloro hydrated aluminum zirconium, pentachloro-hydrated aluminum zirconium or eight aluminum chlorhydrate's zirconiums), the silicon oxide particle of modification is on its surface, and another kind of preferably have a positively charged surperficial silicon oxide particle according to of the present invention.
By processing with aluminum-zirconium hydration complex compound and amino-organosilanes, the silicon oxide particle of modification is another kind ofly preferably according to of the present invention, to have a positively charged surperficial silicon oxide particle on its surface.
In the silicon oxide particle of available types, fumed silica particle is preferred, and it is also referred to as pyrogenic silica.Therefore, aforementioned have positively charged surperficial silicon oxide particle and be preferably based on fumed silica particle.
In the preparation of the silicon oxide particle of this surface modification, for example, pyrogenic silica is added in the solution that is mainly water-based under high shear rate, described solution contains the reaction product that trivalent aluminum compound (for example, Wickenol CPS 325) is preferably reacted with at least one amino-organosilanes.Under applicable condition, obtain the fumed silica dispersion of particles body of UA surface modification.Contain trivalent aluminum compound (as Wickenol CPS 325) and there is high surge capability with the mixture of the reaction product of at least one amino-organosilanes.For example, in alkalescence amino-organosilanes and the hydrochloric acid that forms during the hydrolysis of trivalent aluminum compound (, Wickenol CPS 325).Compare with the modification with Wickenol CPS 325 only, for example, for the aequum of the trivalent aluminum compound (, Wickenol CPS 325) of silica sphere modification much lower.With wherein by the dispersion that Wickenol CPS 325 carries out surface modification, compare, the dispersion of the surface modification of these silicon oxide particles has much lower salts contg.
For example, by amino-organosilanes (is added to trivalent aluminum compound, Wickenol CPS 325) in the aqueous solution, (for example can prepare the trivalent aluminum compound used in surface modification step, Wickenol CPS 325) with the reaction product of at least one amino-organosilanes, or vice versa.Trivalent aluminum compound is carried out 5 minutes to 60 minutes conventionally with reacting of amino-organosilanes at the temperature of 10 ℃ to 50 ℃.Preferably, reaction is at room temperature carried out 10 minutes to 15 minutes.
The reaction product of using trivalent aluminum compound (for example, Wickenol CPS 325) and at least one amino-organosilanes is than using Wickenol CPS 325 to the surface modification of silicon oxide particle method faster to the modifying surface of silicon oxide particle.Therefore, for example,, in the situation on reaction product improved silica surface of using described trivalent aluminum compound (, Wickenol CPS 325) and at least one amino-organosilanes, can shorten modification time or reduce modification temperature.
For example, for the surface modification of using trivalent aluminum compound (, Wickenol CPS 325) with the reaction product of at least one amino-organosilanes, in available silicon oxide particle, pyrogenic SiO 2 particles is particularly preferred.
Can use the mixture of the different SiO 2 powders of the primary granule with different size, replace single pyrogenic silica powder.Use trivalent aluminum compound (for example, Wickenol CPS 325) and the modification procedure of the reaction product of at least one amino-organosilanes to carry out respectively various SiO 2 powders, or utilize the mixture of different SiO 2 powders to carry out simultaneously.
If carry out modification procedure with high shear rate, reaction product is evenly distributed on the surface of silicon-dioxide.In addition, the rheological behavior of dispersion improves.
Preferred trivalent aluminum compound is aluminum chloride, aluminum nitrate, aluminum acetate, al formate, Aluctyl and Wickenol CPS 325.
According to another aspect of the present invention, silicon oxide particle can also comprise at least one aluminum-zirconium hydration complex compound.Preferably, in aluminum-zirconium hydration complex compound, the ratio of zirconium and aluminium is 1: 1 to 1: 7.Preferred aluminum-zirconium hydration complex compound choosing is the group of following composition freely: three aluminum chlorhydrate's zirconiums (CAS98106-53-7), tetrachloro hydrated aluminum zirconium (CAS 98106-52-6), pentachloro-hydrated aluminum zirconium (CAS98106-54-8) or eight aluminum chlorhydrate's zirconiums (CAS 98106-55-9).These complex compounds can be according at US3,903,258 or US 5,179,220 in the process that provides synthetic, or (Rezal 67, Summit Reheis Co or Zirconal L540, BK Giulini GmbH, Ludwigshafen, Germany) that are purchased.According to another aspect of the present invention, silicon oxide particle can comprise at least one compound of the group of the reaction product composition that selects free at least one aforementioned aluminum-zirconium hydration complex compound and at least one amino-organosilanes.
Suitable amino-organosilanes is the amino-organosilanes of formula (I):
R wherein
1, R
2, R
3represent independently hydrogen, hydroxyl, there is the alkyl that does not replace or replace of 1 to 6 carbon atom, the aryl that does not replace or replace, the alkoxyl group that does not replace or replace with 1 to 6 carbon atom or the aryloxy that does not replace or replace.R
4expression is by least one primary, secondary or tertiary amino organic structure part replacing.
Can also use the condensation product of amino-organosilanes to replace above-mentioned monomer amino-organosilanes.Condensation reaction can occur between identical or different amino-organosilanes.
Many known amino-organosilanes enter in those skilled in the art's consideration.The preferred amino-organosilanes that obtains having positively charged surperficial silicon oxide particle for the surface modification of pyrogenic silica is 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, (3-triethoxysilylpropyltetrasulfide)-diethylenetriamine, APTES, N-(2-amino-ethyl)-3-amino-propyl-triethoxysilicane, (3-triethoxysilylpropyltetrasulfide)-diethylenetriamine, normal-butyl TSL 8330, the mixture of at least two kinds in 3-TSL 8330 and these amino-organosilanes.Preferred amino-organosilanes is normal-butyl TSL 8330,3-TSL 8330 or the combination of the two.
Aspect present invention further optimization, for example, in the solution that amino-organosilanes is added to trivalent aluminum compound (, Wickenol CPS 325) before, make its in solution with CO
2reaction, forms organosilane ammonium (that is, the protonated species of amino-organosilanes) and supercarbonate therebetween.By this way, reduce the pH of the reaction mixture of the reaction product that contains trivalent aluminum compound (for example, Wickenol CPS 325) and at least one amino-organosilanes, and increase the surge capability of mixture.Use this process, can reduce the formation of the aluminium by product of undesirable, the undissolvable very high molecular of part.
Its surface with at least one tetravalence zirconium compounds (is for example passed through, zirconyl chloride, zirconium carbonate, zirconium acetate, zirconium lactate), at least one tetravalence zirconium compounds of preferably reacting with at least one amino-organosilanes or the silicon oxide particle of modification is with the reaction product processing of at least one trivalent aluminum compound combination with upper and the two at least one tetravalence zirconium compounds all react with at least one amino-organosilanes, another kind is preferred has a positively charged surperficial silicon oxide particle according to of the present invention.
Similar to the preparation of the silicon oxide particle of the surface modification of the aforementioned reaction product modification by trivalent aluminum compound, carry out the preparation of the silicon oxide particle of this surface modification, but use tetravalence zirconium compounds or at least one tetravalence zirconium compounds react with at least one amino-organosilanes or with at least one trivalent aluminum compound combination with upper at least one the tetravalence zirconium compounds reacting with at least one amino-organosilanes, replacement trivalent aluminum compound.
According to another aspect of the present invention, PCS layer is included in 0.5g/m
2to 25g/m
2amount in scope there is positively charged surperficial silicon oxide particle, preferred 1g/m
2to 20g/m
2, or 2g/m
2to 15g/m
2, or 3g/m
2to 10g/m
2, or 3 to 8g/m
2.Aforementioned quantities is determined conventionally at 50% relative humidity and 20 ℃.
According to another aspect of the present invention, PCS layer thickness is 1 μ m to 50 μ m, preferably 5 μ m to 25 μ m or 10 μ m to 20 μ m.The thickness of PCS layer plane perpendicular to PCS layer at 50% relative humidity and 20 ℃ is determined.
According to another aspect of the present invention, PCS layer comprises at least one tackiness agent.Many types tackiness agent known in the art enters in technician's consideration.
Applicable tackiness agent is water-soluble polymers normally.Particularly preferably be film-forming polymer.
Preferred one group of tackiness agent is the water-soluble polymers as natural polymer and modified product thereof, as the combination of at least two kinds in gelatin, starch, Walocel MT 20.000PV, Natvosol, carboxymethyl cellulose or these polymkeric substance.
In addition, can use the combination of at least two kinds in aforementioned natural glue.
Second preferred one group of tackiness agent is the water-soluble polymers as composite adhesives.In these, following composite adhesives is preferred: the saponification resultant wholly or in part of the multipolymer of polyvinyl alcohol, polyvinylpyrrolidone, vinyl-acetic ester and other monomer; Unsaturated carboxylic acid is as homopolymer or the multipolymer of toxilic acid, (methyl) vinylformic acid or β-crotonic acid etc.; Sulfonate vinyl monomer is as the homopolymer of vinyl sulfonic acid, styrene sulfonic acid or multipolymer; Homopolymer or the multipolymer of the vinyl monomer of (methyl) acrylamide; The homopolymer of other monomer and oxyethane or multipolymer; Urethane; Polyacrylamide; Water-soluble nylon base polymer; Polyester; Polyvinyl lactam; Acrylamide polymer; The polyvinyl alcohol replacing; Polyvinyl acetal; The polymkeric substance of alkyl acrylate and vinylformic acid sulfonated alkyl ester and alkyl methacrylate and methacrylic acid sulfonated alkyl; The polyvinyl acetate of hydrolysis; Polymeric amide; Polyvinylpyridine; Polyacrylic acid; The multipolymer with maleic anhydride; Polyalkylene oxide; The multipolymer that there is the multipolymer of Methacrylamide and there is toxilic acid.The derivative of aforementioned polymer is also preferred.
Preferred composite adhesives is polyvinyl alcohol.Have between 70% to 99%, the degree of hydrolysis between 88% to 98% and 14 especially, 000g/mol to 300, between 000g/mol, especially 100,000g/mol to 200, the polyvinyl alcohol of the weight-average molecular weight between 000g/mol is preferred; The mixture that another preferred aspect of the present invention is at least two kinds of polyvinyl alcohol, described at least two kinds of polyvinyl alcohol are selecting at least one properties difference of the group of free degree of hydrolysis, weight-average molecular weight or the two composition.Character, as weight-average molecular weight and degree of hydrolysis, is provided as technical intelligence by the manufacturers of polyvinyl alcohol.
According to another preferred aspect of the present invention, can use the combination of at least two kinds in aforementioned composite adhesives.In addition can use, the combination of at least one aforementioned composite adhesives and at least one aforementioned natural glue.
According to another aspect of the present invention, tackiness agent can with natural or synthetic high-molecular weight compounds that can not be water-soluble as acrylate latex or with the blend of styrene-acrylate latex.Therefore, can use can not be water-soluble polymkeric substance as tackiness agent or at least as the part of tackiness agent of the present invention.
Preferred another group tackiness agent is reactive polymer.Reactive polymer in the context of the invention is the polymkeric substance with functional group, described functional group can with the article of the group of selecting free adjacent polymer molecules, nano grain surface to form at least one or with it the two be combined to form covalent linkage.Particularly preferred reactive polymer is the polyvinyl alcohol of silanol modification, for example Poval R-polymkeric substance is (as R-1130, R-2105 and R-3109, all by Kuraray Europe GmbH, Frankfurt, Germany provides), the polyvinyl alcohol of carbonyl modification, for example Poval D-polymkeric substance is (as DF-05, DF-17 and DF-20, all by Kuraray Europe GmbH, provided), carboxy-modified polyvinyl alcohol, for example Poval A-polymkeric substance is (as AP-17, AT-17 and AF-17, all by Kuraray Europe GmbH, provided), or the combination of at least two kinds of previous reaction polymkeric substance.In addition can use, the combination of at least one previous reaction polymkeric substance and at least one aforementioned natural or composite adhesives.
Preferably, the group of the free following composition of tackiness agent choosing: the mixture of polyvinyl alcohol and derivative thereof, colloid and derivative thereof, polyvinylpyrrolidone and derivative thereof and at least two kinds of aforementioned adhesion agent.
According to another preferred aspect of the present invention, between PCS layer and layer structure, arrange middle layer.Like this, stratum basale is connected with middle layer with technology by aforementioned manner.Be independent of the type of above-mentioned connection, middle layer is also connected with PCS layer with technology by aforementioned manner.Permitted may the using in the limit of consideration that enters those skilled in the art of eurypalynous middle layer and this middle layer.For example, middle layer can comprise at least one tackiness agent, preferably one or more in aforementioned adhesion agent.
According to another aspect of the present invention, middle layer has the specific refractory power between the specific refractory power of stratum basale and the specific refractory power of PCS layer.
According to another aspect of the present invention, the mole number based on silicon separately, aluminium in PCS layer (Al): the mol ratio of silicon (Si) 0.1 to 10 % by mole, preferably in the scope of 0.5 % by mole to 4 % by mole.The amount of the aforementioned chemical element existing in PCS layer can be determined by many technology well known by persons skilled in the art.Preferred analytical procedure is ultimate analysis.
According to another aspect of the present invention, the mole number based on silicon separately, zirconium in PCS layer (Zr): the mol ratio of silicon (Si) 0.05 % by mole to 2 % by mole, preferably in the scope of 0.1 % by mole to 1 % by mole.The amount of the aforementioned chemical element existing in PCS layer can be determined by many technology well known by persons skilled in the art.Preferred analytical procedure is ultimate analysis.
According to another aspect of the present invention, the PCS layer of layer structure is comprised of following ingredients at least:
I) pyrogenic silica of 65-85 % by weight, positively charged silicon-dioxide or the two;
Ii) at least one of 0.5-10 % by weight comprises aluminium, zirconium or the compound of the two;
Iii) at least one amino-organosilanes of 2-10 % by weight;
Iv) at least one tackiness agent of 5-20 % by weight;
V) at least one stiffening agent of 0.5-4 % by weight;
I wherein) to v) part add up to 100%.For determining that the common method of these values is ultimate analyses.
Stiffening agent in the context of the invention is to make tackiness agent crosslinked to improve the chemical composition of the intensity of layer.
Applicable stiffening agent is preferably according to the type selecting of water-soluble polymers to be hardened.Preferred stiffening agent is organic stiffening agent or inorganic hardener.
Organic stiffening agent is preferably selected from the group being comprised of following: aldehyde, for example oxalic dialdehyde, formaldehyde or glutaraldehyde; Two
alkane, for example 2,3-dihydro two
alkane; Reaction-ity ethylene based compound; Reactive halogen compound; Epoxide; Aziridine; N-methylol compound, for example T10; For example, with two hydrazides, adipic dihydrazide; Or its two or more combination.
Inorganic hardener is preferably selected from the group being comprised of following: chrome alum, aluminium alum, zirconium compounds, divalent metal and boron compound, for example borax or boric acid.Preferred boron compound is boric acid.
According to another aspect of the present invention, can use the combination of at least two kinds in aforementioned organic or inorganic stiffening agent, for example organic and a kind of mineral compound or two kinds of organic compound or two kinds of mineral compound, depend on the water-soluble polymers using in PCS layer separately.
According to another aspect of the present invention, the PCS layer of layer structure has in layer structure minimum specific refractory power in all layers.
According to another aspect of the present invention, a layer structure comprises two above PCS layers, and wherein at least two, the specific refractory power of preferred all PCS layers are lower than the specific refractory power of any other layer in layer structure.
According to another aspect of the present invention, layer structure comprises the additional layer that at least one is adjacent with PCS layer, wherein specific refractory power height at least 0.2 specific refractory power unit (RIU) or at least 0.3RIU or at least 0.4RIU of the refractive index ratio PCS layer of at least one additional layer.Preferably, all layers that are connected with PCS layer have than the specific refractory power height at least 0.2 specific refractory power unit (RIU) of PCS layer or at least 0.3RIU or at least specific refractory power of 0.4RIU.
According to another aspect of the present invention, layer structure comprises one or more adhesion-promoting layers.Many types adhesion-promoting layer known in the art enters in technician's limit of consideration.Layer structure preferred at least one, also more preferably all adhesion-promoting layers comprise one or more above-mentioned tackiness agents.According to another preferred aspect of the present invention, adhesion-promoting layer can be arranged on stratum basale.Many types adhesion-promoting layer known in the art enters in technician's limit of consideration, those that especially use in photographic industry.Preferably, can process the adhesivity improving substrate by Corona discharge Treatment or corona-aerosol.
According to another aspect of the present invention, layer structure comprises adjacent one another are:
(a1) stratum basale;
(b1) PCS layer; With
(c1) at least four additional layers,
The first layer in additional layer is adjacent with PCS layer,
Wherein the specific refractory power height at least 0.01 specific refractory power unit of one deck before the refractive index ratio of each additional layer, preferred at least 0.02 specific refractory power unit, and
Wherein the refringence between the additional layer of outermost and PCS layer is 0.6 specific refractory power unit at the most, preferably 0.5 specific refractory power unit or at the most 0.4 specific refractory power unit at the most.
According to another aspect of the present invention, layer structure comprises adjacent one another are:
(a1) stratum basale;
(b1) at least four additional layers; With
(c1) PCS layer;
The first layer and stratum basale in additional layer are adjacent,
The wherein low at least 0.01 specific refractory power unit of specific refractory power of one deck before the refractive index ratio of each additional layer, preferred at least 0.02 specific refractory power unit, and
Wherein the refringence between PCS layer and the first additional layer is at the most-0.6 specific refractory power unit, preferably at the most-0.5 specific refractory power unit or at the most-0.4 specific refractory power unit.
According to another aspect of the present invention, the average directly transmissivity of PCS layer is greater than 90%, is greater than 94%, is greater than 95%, is greater than 96%, is greater than 97% or be greater than 98%.Therefore, the average directly transmissivity of PCS layer is in 90 to 99.99% scope, preferably in 94 to 99.9%, 95 to 99.9%, 96 to 99.9%, 97 to 99.8% or 98 to 99.5% scope.
Average directly transmissivity is used the optical measurement of the different wave length between λ=350nm to λ=800nm according to the method for the following stated.For the data point of each collection, the difference of light wavelength and front one-shot measurement is Δ λ=1nm.Average directly transmissivity is defined in the mean average value (mean average) of the value of the data of collecting in these measurements.
According to another aspect of the present invention, the average diffuse transmittance of PCS layer is less than 4%, is preferably less than 3.5%, is less than 3%, is less than 2.5 or be less than 2.0%.Conventionally, still have 0.2% or 0.5% or the diffuse transmittance of more PCS layer.
Diffuse transmittance is used the optical measurement of the different wave length between λ=350nm to λ=800nm according to the method for the following stated.For the data point of each collection, the difference of light wavelength and front one-shot measurement is Δ λ=1nm.Average diffuse transmittance is defined in the mean average value (mean average) of the value of the data of collecting in these measurements.
According to another aspect of the present invention, the PCS layer of layer structure comprises at least one another kind of particle, and wherein another kind of particle is preferably pigment or light diffusion particle or the combination of the two.At least one another kind of particle is preferably inorganic particulate or organic filler.Many known inorganic particulates enter in those skilled in the art's limit of consideration.Preferably, the group of the free following composition of inorganic particulate choosing: titanium dioxide, more preferably rutile-type or Detitanium-ore-type, zinc oxide, zinc sulphide and barium sulfate or its two or more combination.Preferably, organic filler is porous or non-porous.
Term diffusion particle in the context of the invention refers to the particle with such size and/or shape: the light that wavelength X is 350nm to 800nm is at least in part in the place's scattering of described particle, thereby with respect to entering total amount layer, light in 350nm to 800nm scope that comprises described particle, in the amount of the light of described particle place's scattering, be preferably at least 10%.
The PCS layer that also comprises at least one another kind of aforementioned particles is also referred to as structured layer, and the median size of wherein said another kind of aforementioned particles is larger than the median size of the silicon oxide particle of PCS layer.
According to another aspect of the present invention, layer structure comprises at least one layer, and described layer has at least one patterned layer surface.Patterned layer surface in the context of the invention is preferably by acquisitions such as embossing, etchings.Being formed on the structured layer that another kind of aforementioned particles is wherein greater than average layer thickness is another kind of patterned layer.
According to another aspect of the present invention, at least one additional layer of layer structure comprises the freely composition of the group of following composition of choosing: fluoropolymer, polymkeric substance, magnesium fluoride, Sodium Fluoride or its combination of at least two kinds.Conventionally, this additional layer has the specific refractory power that is greater than 1.2.
According to another aspect of the present invention, PCS layer can also comprise tinting material, the light of described tinting material absorbing wavelength in 200nm to 2500nm scope.These tinting materials are preferably organic or inorganic compound or its combination of at least two kinds.Aforementioned tinting material can exist with the form of molecule or the form of particle in PCS layer.
According to another aspect of the present invention, PCS layer can also contain the freely luminophore of the group of following composition of choosing: organic molecule, organic pigment, organic polymer, inorganic particulate or the nano particle that luminophor is contained in portion within it.Luminophore in the context of the invention sends the light of wavelength in 200nm to 2500nm scope.
Another aspect of the present invention is that described method comprises at least following method steps for the preparation of the method with the layer structure of substrate and preferably transparent PCS layer:
(I) provide stratum basale, it is preferably transparent;
(II) to described stratum basale stack PCS layer,
Wherein said PCS layer comprises many silicon particles,
Wherein said silicon oxide particle has positively charged surface;
(III) optionally at least one additional layer is superimposed on described stratum basale.
Preferably, the specific refractory power of described PCS layer is less than 1.2.More preferably, the specific refractory power that comprises the layer structure of PCS layer and additional layer (if there is) is less than 1.2.
Preferred aspect for the preparation of layer structure method of the present invention, described aspect relates to layer structure as the component characteristic of stratum basale, PCS layer, its assembly, and according to any other aspect of based on context describing above of the layer structure of the present invention of first aspect present invention and other aspect, be all combined in herein.
If additional layer is superimposed to stratum basale, can be to arrange additional layer with respect to stratum basale and the two different mode of PCS layer.Therefore, the additional layer that is superimposed to stratum basale can be arranged to.
(i) make additional layer and stratum basale be arranged in the offside of PCS layer;
(ii) additional layer is arranged between stratum basale and PCS layer; Or
(iii) make additional layer and PCS layer be arranged in the offside of stratum basale.
Preferably, the additional layer that is superimposed to stratum basale is arranged to additional layer and stratum basale are arranged in the offside of PCS layer.
According to another aspect of the present invention, by the following step at least, carry out the step (II) of described method:
I. preparation comprises many liquid phases with positively charged surperficial silicon oxide particle He at least one liquid;
Ii. with 4 to 200g/m
2, preferably 8 to 150g/m
2, or 15 to 125g/m
2, 25 to 80g/m
2, or 25 to 65g/m
2scope in amount liquid phase is applied on stratum basale; And afterwards
Iii. be dried the coating forming in step I i., obtain described PCS layer (3).
According to another aspect of the present invention, in the step (II) of described method, by the liquid phase that is preferably the dispersion liquid that comprises silicon oxide particle and liquid, apply additional layer.In the context of the invention, term dispersion liquid has been described a kind of system, and wherein the discontinuous phase of at least one the first component is dispersed in the external phase of at least one other component.Conventionally, facilitating at least one component of discontinuous phase is particulate matter.External phase conventionally not with discontinuous phase in identical physical condition.The two can comprise one or more components independently of one another external phase and discontinuous phase.
Can be according to step I. obtain comprising many liquid phases with positively charged surperficial silicon oxide particle, for example, by conventional diverting device as
ystral
deng.Can use separately aforementioned means, or can parallel connection or series combination use two or more types.
Preferably, in aforementioned liquid phase, at least one liquid is water.According to another preferred aspect of the present invention, liquid phase comprises the mixture more than a kind of liquid, preferred at least two kinds of liquid, and wherein, also preferred, the liquid phase that is greater than 50 % by weight is water, the gross weight of described % by weight based on liquid phase.
According to another preferred aspect of the present invention, the liquid phase that comprises two kinds of liquid that are at least selected from aforementioned group, comprise the water between at least 75 % by weight, preferred at least 80 % by weight or at least 90 % by weight or 94 to 99.5 % by weight, each percentage ratio is the gross weight based on liquid ions in liquid phase all.
Step I i. can complete by extrusion coated, airblade coating, scraper for coating, slit pearl coating (slot bead coating), sliding pearl coating (slide bead coating) and curtain coating.Preferred method is sliding pearl coating and curtain coating.Preferably, step I i. carries out at least in part at the temperature of 20 ℃ to 60 ℃ or 25 ℃ to 50 ℃ or 30 ℃ to 40 ℃.Preferably, with the speed of approximately 20 to approximately 400 ms/min, carry out coating process.
Step I ii. can, at the temperature of 2 ℃ to 90 ℃, under 10% to 80% relative humidity, carry out the time of 30 seconds to 10 minutes.If step I ii. comprises two above sub-steps, between each step, temperature, relative humidity and time can change, and they are independently of one another in aforementioned temperature scope, humidity range and time range.
According to another aspect of the present invention, the silicon oxide particle of described method comprises freely at least one compound of group of following composition of choosing: the reaction product of the reaction product of the reaction product of trivalent aluminum compound, tetravalence zirconium compounds, amido organosilicon hydride compounds, at least one trivalent aluminum compound and at least one amido organosilicon hydride compounds, at least one tetravalence zirconium compounds and at least one amido organosilicon hydride compounds, at least one trivalent aluminum compound and at least one tetravalence zirconium compounds and at least one amido organosilicon hydride compounds and combination thereof.With respect to a first aspect of the present invention and other aspect, described preferred aspect, and it is combined in herein.This is also applicable to carry out according to it mode of the modification of silicon oxide particle.
Much known liquid is usingd its mixture and is entered in limit of consideration as the continuing phase of aforementioned liquid phase.According to an aspect of the present invention, liquid select free water, alcohol, and composition thereof the group that forms.Preferably, select water as liquid.Also preferred, the dispersion liquid being obtained by the surface modification of silicon oxide particle is directly used in the preparation of described dispersion liquid, applies described dispersion liquid to form additional layer in the step (II) of described method.
According to another aspect of the present invention, liquid phase contains 5%, is preferably less than 2% volatile organic solvent.In the context of the invention, volatile organic solvent is organic compound, and it is liquid under 20 ℃, 1013hPa, and has the vapour pressure that is less than the initial boiling point of 250 ℃ or is greater than 0.27kPa (2mm Hg) at 25 ℃ or the two.
According to another aspect of the present invention, liquid phase comprises at least one tackiness agent.With respect to a first aspect of the present invention, described preferred aspect, and it is combined in herein.
According to another aspect of the present invention, the liquid phase of described method can comprise additional component, if pH regulator material, antioxidant, stablizer, stain control agent, sanitas, softening agent, rheology modifier are as thinner and/or thickening material, membrane-forming agent, filler.The aforementioned additional component of the liquid phase of described method can be added in liquid phase as the aqueous solution.If one or more in these compounds can not be fully water-soluble, can they be bonded in liquid phase by other common technology as known in the art, for example, for example, can be by the water-soluble mixable solvent of these compounds, in lower alcohol, glycol, ketone, ester or acid amides.Alternatively, can be using compound as fine dispersions, as emulsion or as cyclodextrin inclusion compound, join in the liquid phase of described method, or be bonded in latex particle, and in the liquid phase of described method, form another group particle.
In the art, known many technology are coated to the layer that comprises particle on stratum basale.Therefore, those skilled in the art will be identified for, in the step (II) in described method, the PCS layer that comprises many silicon oxide particles is coated to the proper technology on stratum basale.
According to another aspect of the present invention, in method steps (II), by extrusion coated, airblade coating, scraper for coating, stepwise coating or curtain coating, apply PCS layer and optional additional layer.Can also use spraying technique to apply PCS layer and optional additional layer.In addition, can on PCS layer, be accumulated as extra play by several individual layers, described several individual layers can be coated with successively or simultaneously.Can also be with PCS layer, additional layer or extra play or its combination coated base bottom of at least two kinds on more than one surface.More preferably, in a side of stratum basale, be coated with antistatic layer or non-curl backing, it is back to PCS layer.The preferred coating process that applies PCS layer and optional additional layer in step (II) is stepwise coating or curtain coating, wherein PCS layer, optional additional layer and other possible extra plays is applied on stratum basale simultaneously.More preferably, carry out the application step in method of the present invention, thereby be coated with two single coating of carrying out continuously above in single coating mode, and it is multi-layer coated with One-through design, to carry out the while.Yet the coating process of quoting should not think to limit the present invention.
Another aspect of the present invention is the layer structure that can obtain by the method for the preparation of layer structure as above.
According to another aspect of the present invention, layer structure comprises
(a) stratum basale; With
(b) be superimposed at least in part the PCS layer of stratum basale, described PCS layer comprises many positively charged surperficial silicon oxide particles (4) that have,
The specific refractory power of wherein said PCS layer is less than 1.2.
In the context of the aforementioned method for the preparation of layer or the preferred aspect of describing in the context of aforementioned layers structure is combined in herein.
According to another aspect of the present invention, the cumulative volume based on layer, the pore volume of the PCS layer of layer structure is in the scope of 55 to 80 volume %.
According to another aspect of the present invention, the PCS layer of layer structure is transparent layer, thermal insulation layer, low-index layer or its combination of at least two kinds.
Another aspect of the present invention is the optics that comprises the preferred aspect of aforementioned layers structure or aforementioned layers structure.
Preferably, the group of the free following composition of optics choosing: luminescent device, photocon, optical transform device, optical recording device and electric insulation layer or its two or more combination.
Many known optics that are selected from above-mentioned group enter in those skilled in the art's limit of consideration.Preferred luminescent device choosing is the group of following composition freely: face plate illumination, plate lighting, floodlight, headlight, spot light lamp and electronic console.Preferred photocon choosing is the group of following composition freely: plane and on-plane surface photoconduction.Preferred optical transform device choosing is the group of following composition freely: convertor of colors and colour filter.Preferred optics is antireflection device and light diffuser part.In addition the two or more system in, can the aforementioned optics of Selection and Constitute.In these, system is as preferred in indicating meter indicating meter, photographic camera and projector.
Another aspect of the present invention be contain have positively charged surperficial silicon oxide particle layer for optical application, in particular for the purposes of photovoltaic applications.
Following examples are served as exemplary illustration of the present invention and should be interpreted as restriction.
Accompanying drawing is described
Exemplify in the accompanying drawings theme of the present invention.Yet accompanying drawing is not intended to limit by any way the scope of the present invention or claim.
With reference to Fig. 1, a layer structure (1) is shown.Layer structure comprises stratum basale (2) and PCS layer (3).PCS layer comprises silicon oxide particle (4).
With reference to Fig. 2, another layer of structure (1) is shown.Identical with in Fig. 1, layer structure comprises stratum basale (2) and PCS layer (3).PCS layer comprises silicon oxide particle (4).In aspect preferred (optional), middle layer (5), as adhesion-promoting layer, can be arranged between stratum basale (2) and PCS layer (3).In aspect preferred (optional), extra play (6), as luminescent layer or diffusion layer etc., can be arranged in a side of PCS layer, and it is back to stratum basale (2).
In Fig. 3, method of the present invention is shown.
In Fig. 4, optics of the present invention (7) is shown.Optics (7) comprises a layer structure (1).Optics (7) and layer structure (1) are positioned in light path (9).Optics (7) can also comprise opening (8), and light can be advanced by optics (7) via described opening (8) in light path (9).
In Fig. 5, another layer of structure (1) is shown.Identical with in Fig. 1, layer structure comprises stratum basale (2) and PCS layer (3).PCS layer comprises silicon oxide particle (4).This layer structure comprises four additional layers (6,10), comprises " outermost " additional layer (10).With respect to front one deck, each additional layer (6,10) has than the specific refractory power of the high 0.02 specific refractory power unit of the specific refractory power of front one deck.The high 0.08 specific refractory power unit of specific refractory power of the refractive index ratio PCS layer (3) of the additional layer of outermost (10).
Testing method
A. specific surface area
By as by S.Brunauer, P.H.Emmet and J.Teller are at " Adsorption of Gases in Multimolecular Layers (gas adsorption in polymolecular layer) ", Journal of the American Chemical Society (American Chemical Society's periodical) 60, p.309-319 the BET isothermal method described in (1938), determines specific surface area.
B. particle diameter and polydispersity index
Utilize disc centrifuge CPS DC24000, use the gradient of 8 % by weight to 24 % by weight sucrose, determine size distribution.After forming gradient, will proofread and correct standard substance (, by CPS Instruments, Inc. provides for PVC calibration standard product, 0.377 μ m in deionized water) and be injected in the centrifugal pan with 20000rpm rotation.Temperature is that 22 ℃ and relative humidity are 48%.
Once proofreaied and correct, the first sample that is about to studied dispersion liquid with 0.5 % by weight (solid, all the other: concentration water) is injected in centrifugal pan (with 20000rpm rotation), so that saccharose gradient is stable.Afterwards by three extra same sample with 0.5 % by weight (solid, all the other: the injection of same concentrations water), each sample is drawn a diagram automatically.Pictorialization particle diameter (representing with μ m) and the weight distribution representing with % by weight on y axle on x axle.Integration by weight distribution curve obtains median size d
50(with nm, representing).According to weight-average diameter (D
w) and number average diameter (D
n) between ratio, the polydispersity index (PDI) of calculation sample:
N
idiameter D
ithe quantity of particle.The d providing in embodiment
50the value of-diameter and polydispersity index is three mean numbers of measuring.
By CPS software, automatically carry out d
50the calculating of-diameter and polydispersity index.
C. article, for example thickness of layer, layer structure
For each sample, utilize and be equipped with the Leica RM2245 rotary microtome of narrow blade (low profile blade) Leica819 to obtain thin section.The width of thin section is 35 μ m.With opticmicroscope Zeiss Axiophot and Zeiss Epiplan Neofluar20x object lens, check thin section afterwards.With JVC KY-F70B Tri-CCD camera (1360x1024 pixel resolution), take pictures, and use the software analySIS3.1 being provided by Soft Imaging System to determine layer thickness.The tolerance range of thickness measurement is ± 1 μ m.In a plurality of samples of each embodiment, only have the layer of the thickness of thickness within the scope of 14-17 μ m qualified for further evaluation.
D. zeta-potential and iso-electric point
On Dispersion Technology DT1200 instrument, carry out zeta-potential titration." sample chamber " is by 100ml beaker, magnetic stirring apparatus, two syringes and five sensors: sound, cvi (colloid oscillating current), temperature, pH and specific conductivity form.By cvi and sound transducer, obtain zeta-potential.At room temperature measure, and be 2 % by weight SiO by silica dispersions dilution
2to avoid in iso-electric point gelation around.The starting point of titration curve is dispersion liquid pH, and according to it, via syringe, adds hydrochloric acid 0.1mol/L or sodium hydroxide 0.1mol/L.Between about pH11 of the extremely positively charged silica dispersions of initial pH, and between about pH3 of negatively charged ion silica dispersions, carry out titration at initial pH.Chart by zeta-potential as the function of pH, reads the zeta-potential of YimVWei unit at pH5 and iso-electric point.
E. pore volume
Three-step approach via the liquid absorption capacity of the porous material based on as described below, obtains the pore volume in layer.This pore volume can be filled by air or any other gas.
The first step: stoste absorbs
For each embodiment, utilize and the identical process of describing in following examples, but with 140g/m
2wet coating wt the resin coating base portion for ink-jet media (can be from Schoeller GmbH & Co.KG, Osnabr ü ck, Germany obtains, thickness 252 μ m, weight (263 ± 5) g/m
2, be primed with 71mg/m
2gelatin coating), three A3 paper of coating base portion.In baking oven, after 30 ℃ are dried 60 minutes, from the centre of every coating A3 paper, cut A4 paper.These A4 paper are regulated to 24 hours in baking oven at 40 ℃.Afterwards, on the balance Mettler PM-3600Delta Range of laboratory, three A4 paper are weighed, and calculate the weight in average of every square metre of the A4 sample of coating base portion.
Afterwards, in the foregoing manner cut from base portion 10 A4 paper (as paid) are weighed, to obtain the weight in average of the A4 paper of base portion.The weight in average of every square metre of base portion is 265.3g/m
2.
By deducting the weight in average of the A4 paper of base portion the weight in average from coating A4 paper, obtain the weight in average of drying layer.According to the composition of the weight in average of drying layer and layer, determine the weight in average of the silicon-dioxide of every coating A4 paper, and calculate the weight in average of the silicon-dioxide of every square metre of overlay paper.
Afterwards, utilize to be equipped with two groups of rotary squeezing roller automated installations, make each ethylene glycol through 30 % by weight in three A4 paper of coating matrix solution in deionized water.The A4 paper of coating matrix is inserted between the roller of first group, and pushes in liquid.When paper is immersed in liquid completely, second group of roller pulled out them and remove excessive liquid.Again paper is weighed afterwards.According to three result calculating mean values.This is the weight in average of coating matrix and absorbed liquid.By deducting the weight in average of the dry coating matrix obtaining above, obtain the weight in average of absorbed liquid (not containing coating matrix) afterwards.Finally, according to the density (1.038g/cm of absorbed liquid
3), calculate the average-volume of the absorbed liquid of every square metre of coating matrix.
Second step: by the liquid-absorbent of matrix and tackiness agent
Because the back side of PVA tackiness agent and coating matrix and positive some liquid that absorb, prepare second group of 10 A3 sample in mode as hereinbefore, but use 5.88g/m
2the coating of Poval PVA235 (poly (vinyl alcohol) binder, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) and 1.03g boric acid.In baking oven, after 30 ℃ are dried 60 minutes, in the middle of every A3 coating sample, cut A4 paper.10 A4 paper are regulated to 24 hours in baking oven at 40 ℃.Afterwards 10 A4 paper are carried out and identical before absorption process, and obtain the average-volume of every square metre of liquid being absorbed by front, the back side and PVA layer.
In addition, the 3rd group of 10 samples of matrix (as paid) are absorbed to test.This has obtained the weight of the liquid being absorbed by recto and the back side.According to this value, obtain the average-volume of every square metre of liquid being absorbed by the front and back of uncoated matrix.The average-volume of the liquid by the absorption from second group (back side+front+PVA) deducts the average-volume of liquid of the absorption in the 3rd group (back side+front), obtains the average-volume of the liquid that absorbed by PVA tackiness agent.According to this value, the average-volume of calculating the liquid that every gram of PVA tackiness agent absorbs is 0.19ml/g PVA.According to the amount of tackiness agent in layer, for each embodiment, determine the average-volume of every square metre of liquid being absorbed by PVA tackiness agent.
The 3rd step: the volume of air of drying layer
For each sample, in the cumulative volume of the liquid by the absorption that obtains, deduct afterwards the average-volume of the liquid being absorbed by PVA tackiness agent and by the back side and the positive average-volume absorbing of uncoated matrix from first group, obtain the average-volume of the liquid that the hole by layer absorbs.According to this value, finally calculate the average air volume of every gram of silicon-dioxide in drying layer.
F. specific refractory power
Refractive index n by volume fraction and every kind of component (comprising air)
d 20calculate refractive index n
d 20:
The refractive index n of layer
d 20=∑ (specific refractory power of the volume fraction * X of component X)
Data based on providing in following table, exemplify the refractive index n in embodiment 1 middle level
d 20calculating (at 20 ℃, Na-D line):
Therefore, there is 10.1cm
3/ m
2the pore volume of drying layer and the specific refractory power of the layer of the embodiment 1 of the volume of air of 63 volume % be:
N
d 20(layer)=(0.23*1.459+0*1.577+0.06*1.43+0.06*1.53+0.01*1.456+0.0*1. 51+0.63*1.001)=1.17
G. transmissivity measurement
Use is equipped with the spectrophotometer Varian Cary100bio of integrating sphere (integration sphere) Labsphere DRA-CA-301 to carry out transmissivity measurement.The spectral range of transmissivity measurement is 350-800nm, and resolving power is 1nm.
Integrating sphere is for measuring the transmission of the sample of total transmission mode and diffuse transmission mode.In order to measure total transmission, integrating sphere is equipped with Spectralon scatterer.In order to measure diffuse transmission, integrating sphere is equipped with ligh trap.By deduct diffuse transmission from total transmission, obtain direct transmission (perpendicular to the transmission of sample).
Sample to be measured is placed on to the ingress of integrating sphere, makes aspect to integrating sphere (first surface that light is in contact with it is the back side of sample).
For the photoabsorption of PET base material, proofread and correct total transmission value and diffuse transmission value.
Use derives from the equation of Beer-Lambert law (Beer-Lambert law), for the slight variation of layer thickness, proofreaies and correct direct transmission:
The thickness of object of reference is 16 μ m (corresponding to the thickness of embodiment 1 and comparative example 1).
H. viscosity
With Bohlin CVO-50 mobilometer at 227s
-1shearing rate and the temperature of 40 ℃ under carry out viscosity measurement.
I.pH
With standard compound glass pH electrode, at 40 ℃, measure pH.
Embodiment
embodiment 1
The positively charged SiO that contains 24 % by weight
2aqueous liquid dispersion
By the Wickenol CPS 325 of 3.51g (Locron P, can be from Clariant AG, Muttenz, Switzerland acquisition), (Dynasilan 1189 for the 10 % by weight solution of formic acid of 4.1g boric acid, 18.4g and the normal-butyl aminopropyl trimethyl silane of 26.0g, 98%, can be from Degussa AG, D ü sseldorf, Germany obtains) in 5 ℃ of deionized waters that are added to successively 695.4g under mechanical stirring.Continuously stirring in during 15 minutes.By the specific surface area of 240g, be 300m
2the pyrolytic silicon dioxide of/g (Cab-O-Sil H5, can be from Cabot Corp., Billerica, USA obtains) at 5 ℃, under violent mechanical stirring, be added in this dispersion liquid.Afterwards, 5 % by weight solution of the bicarbonate of ammonia of 12.63g (Fluka AG, Buchs, Schweiz) are being added in dispersion liquid under mechanical stirring continuously.With rotor-stator high shear mixer, this dispersion liquid is further stirred 10 minutes.During 15 minutes, temperature is increased to 40 ℃, makes afterwards dispersion liquid be cooled to room temperature.Finally, make dispersion liquid by take 45 volume %, be filled with the ball mill Dyno-Mill Multi-Lab (WAB AG Maschinenfabrik) of the zirconium oxide bead that diameter is 0.8-1.0mm with 1.5 liters/h.
In following table, provided the character of this dispersion liquid:
| pH/40℃ | 5.6 |
| At 227s -1The viscosity of/40 ℃ | 92mPas |
| d 50-particle diameter (CPS) | 53nm |
| Polydispersity (CPS) | 1.58 |
| Zeta-potential at pH5 | 42mV |
| Iso-electric point | pH8.9 |
The coating solution that contains the positively charged silicon-dioxide of 14.8 % by weight
Poval PVA235 (the poly (vinyl alcohol) binder that adds 63.4g at 40 ℃ of above-mentioned dispersion liquids to 123.3g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) tensio-active agent Olin G (the Arch Chemicals of 7 % by weight solution, 2.88g, Norwalk, USA) 5.26 % by weight solution and 10.5g deionized water.The pH of this coating solution is 5.45 and it is at 227s
-1viscosity be 98mPas.Ratio between PVA tackiness agent and silicon-dioxide is 15: 100 (w/w).
Matrix
" matrix " Shi You supplier pays has 400mg/m
2the transparent polyester carrier (Agfa P175, thickness 175 μ m) of gelatin adhesion-promoting layer.
Coating in transparent polyester matrix.
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 16.0 μ m.The pore volume of drying layer is 10.1cm
3/ m
2(it is corresponding to 63% volume of air) and the refractive index n calculating
d 20be 1.17.
embodiment 2
The positively charged SiO that contains 25 % by weight
2aqueous liquid dispersion
By the Wickenol CPS 325 of 12.78g (Locron P, can be from Clariant AG, Muttenz, Switzerland obtains) and the normal-butyl aminopropyl trimethyl silane (Dynasilan1189 of 21.0g, 98%, can be from Degussa AG, D ü sseldorf, Germany obtains) in 5 ℃ of deionized waters that are added to successively 716.2g under mechanical stirring.Continuously stirring in during 15 minutes.By the specific surface area of 250g, be 300m
2the pyrolytic silicon dioxide of/g (Cab-O-Sil H5, can be from Cabot Corp., Billerica, USA obtains) at 5 ℃, under violent mechanical stirring, be added in this solution.With rotor-stator high shear mixer, this dispersion liquid is further stirred 10 minutes.During 60 minutes, temperature is increased to 50 ℃, makes afterwards dispersion liquid be cooled to room temperature.Finally, make dispersion liquid by take 45 volume %, be filled with the ball mill Dyno-Mill Multi-Lab (WAB AG Maschinenfabrik) of the zirconium oxide bead that diameter is 0.8-1.0mm with 1.5 liters/h.
In following table, provided the character of this dispersion liquid:
| pH/40℃ | 5.3 |
| At 227s -1The viscosity of/40 ℃ | 45mPas |
| d 50-particle diameter (CPS) | 53nm |
| Polydispersity (CPS) | 1.60 |
| Zeta-potential at pH5 | 43mV |
| Iso-electric point | pH8.7 |
The coating solution that contains the positively charged silicon-dioxide of 14.8 % by weight
Poval PVA235 (the poly (vinyl alcohol) binder that adds 580mg boric acid, 63.4g at 40 ℃ of above-mentioned dispersion liquids to 118.4g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) tensio-active agent Olin G (the Arch Chemicals of 7 % by weight solution, 2.88g, Norwalk, USA) 5.26 % by weight solution and 14.7g deionized water.The pH of this coating solution is 4.71 and it is at 227s
-1viscosity be 70mPas.Ratio between PVA tackiness agent and silicon-dioxide is 15: 100 (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 15.4 μ m.The pore volume of drying layer is 9.8cm
3/ m
2(it is corresponding to 63% volume of air of drying layer) and the specific refractory power of calculating are 1.17.
comparative example 1
The electronegative SiO that contains 13.5 % by weight
2aqueous liquid dispersion
By the specific surface area of 135g, be 300m
2the pyrolytic silicon dioxide of/g (Cab-O-Sil H5, can be from Cabot Corp., Billerica, USA obtains) is in the 1N solution and 852.2g deionized water of 5 ℃ of sodium hydroxide that are added to 12.8g under violent mechanical stirring.With rotor-stator high shear mixer, this dispersion liquid is further stirred 10 minutes.During 60 minutes, temperature is increased to 60 ℃, makes afterwards dispersion liquid be cooled to room temperature.Finally, make dispersion liquid by take 45 volume %, be filled with the ball mill Dyno-Mill Multi-Lab (WAB AG Maschinenfabrik) of the zirconium oxide bead that diameter is 0.8-1.0mm with 1.5 liters/h.
In following table, provided the character of this dispersion liquid:
| pH/40℃ | 8.2 |
| At 227s -1The viscosity of/40 ℃ | 105mPas |
| d 50-particle diameter (CPS) | 96nm |
| Polydispersity (CpS) | 2.54 |
| Zeta-potential at pH5 | -12mV |
| Iso-electric point | 3.8 |
The coating solution that contains the electronegative silicon-dioxide of 10.0 % by weight
At 40 ℃ of above-mentioned dispersion liquids to 148.2g, add 4 % by weight solution of the boric acid of 3.0g, the Poval PVA235 (poly (vinyl alcohol) binder of 42.8g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) tensio-active agent Olin G (the Arch Chemicals of 7 % by weight solution, 2.88g, Norwalk, USA) 5.26 % by weight solution and 3.1g deionized water.The pH of this coating solution is 7.64 and it is at 227s
-1viscosity be 80mPas.Ratio between PVA tackiness agent and silicon-dioxide is 15: 100 (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 75g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 16.0 μ m.The pore volume of drying layer is 11.1cm
3/ m
2(it is corresponding to 70% volume of air of drying layer) and the specific refractory power of calculating are 1.14.
comparative example 2
The coating solution of the aluminum oxide/aluminium hydroxide that contains 18.6 % by weight
In 41.6g deionized water, add successively 9 % by weight solution of the lactic acid of 3.4g, aluminum oxide/aluminium hydroxide HP14/4 (Sasol GmbH of 18.6g, Brunsb ü ttel, Germany), the Poval PVA235 (poly (vinyl alcohol) binder of 31.0g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, tensio-active agent Triton X-100 (the Sigma Corp. of the glycerine of 9 % by weight solution high-polymerization degree), 50 % by weight of 0.16g and 1.21g, St-Louis, USA) 10 % by weight solution.With Vltrasonic device, will in coating solution is during 3 minutes, disperse.Finally, add 4.0g boric acid 10 % by weight solution and utilize deionized water to make weight reach 100g.
In following table, provided the character of this coating solution:
| pH/40℃ | 3.5 |
| At 227s -1The viscosity of/40 ℃ | 41mPas |
| d 50-particle diameter (CPS) | 46nm |
| Many 9 divergences (CpS) | 1.24 |
| Zeta-potential at pH5 | 32mV |
| Iso-electric point | 7.4 |
Ratio between PVA tackiness agent and aluminum oxide/aluminium hydroxide is 15% (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 75g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 15.1 μ m.The pore volume of drying layer is 8.2cm
3/ m
2(it is corresponding to 54% volume of air of drying layer) and the specific refractory power of calculating are 1.29.
comparative example 3
The coating solution of the aluminum oxide/aluminium hydroxide that contains 18.6 % by weight
In 41.6g deionized water, add successively 9 % by weight solution of the lactic acid of 3.4g, aluminum oxide/aluminium hydroxide Cataloid AP-3 of 18.6g (JGC Catalysts & Chemicals Ltd, Kawasaki, Japan), the Poval PVA235 (poly (vinyl alcohol) binder of 31.0g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, tensio-active agent Triton X-100 (the Sigma Corp. of the glycerine of 9 % by weight solution high-polymerization degree), 50 % by weight of 0.16g and 1.21g, St-Louis, USA) 10 % by weight solution.With Vltrasonic device, will in coating solution is during 3 minutes, disperse.Finally, add 4.0g boric acid 10 % by weight solution and utilize deionized water to make weight reach 100g.
In following table, provided the character of this coating solution:
| pH/40℃ | 4.0 |
| At 227s -1The viscosity of/40 ℃ | 67mPas |
| d 50-particle diameter (CPS) | 45nm |
| Polydispersity (CpS) | 1.31 |
| Zeta-potential at pH5 | 31mV |
| Iso-electric point | 9.2 |
Ratio between PVA tackiness agent and aluminum oxide/aluminium hydroxide is 15% (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 75g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 13.7 μ m.The pore volume of drying layer is 7.3cm
3/ m
2(it is corresponding to 53% volume of air of drying layer) and the specific refractory power of calculating are 1.29.
embodiment 3
The positively charged SiO that contains 23 % by weight
2aqueous liquid dispersion
By eight hydration zirconyl chloride (the Fluka AG of 13.9g, Buchs, Schweiz), (Dynasilan 1189 for the normal-butyl aminopropyl trimethyl silane of 4.5g boric acid and 27.0g, 98%, can be from Degussa AG, D ü sseldorf, Germany obtains) in 5 ℃ of deionized waters that are added to successively 724.6g under mechanical stirring.Continuously stirring in during 15 minutes.By the specific surface area of 230g, be 300m
2the pyrolytic silicon dioxide of/g (Cab-O-Sil H5, can be from Cabot Corp., Billerica, USA obtains) at 5 ℃, under violent mechanical stirring, be added in this solution.With rotor-stator high shear mixer, this dispersion liquid is further stirred 10 minutes.During 60 minutes, temperature is increased to 50 ℃, makes afterwards dispersion liquid be cooled to room temperature.Finally, make dispersion liquid by take 45 volume %, be filled with the ball mill Dyno-Mill Multi-Lab (WAB AG Maschinenfabrik) of the zirconium oxide bead that diameter is 0.8-1.0mm with 1.5 liters/h.
In following table, provided the character of this coating solution:
| pH/40℃ | 4.3 |
| At 227s -1The viscosity of/40 ℃ | 63mPas |
| d 50-particle diameter (CPS) | 59nm |
| Polydispersity (CpS) | 1.67 |
| Zeta-potential at pH5 | 40mV |
| Iso-electric point | pH9.0 |
The coating solution that contains the positively charged silicon-dioxide of 14.8 % by weight
Poval PVA235 (the poly (vinyl alcohol) binder that adds 63.4g at 40 ℃ of above-mentioned dispersion liquids to 128.7g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) tensio-active agent Olin G (the Arch Chemicals of 7 % by weight solution, 2.88g, Norwalk, USA) 5.26 % by weight solution and 5.0g deionized water.
The pH of this coating solution is 4.4 and it is at 227s
-1viscosity be 61mPas.Ratio between PVA tackiness agent and silicon-dioxide is 15: 100 (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 13.8 μ m.The pore volume of drying layer is 8.6cm
3/ m
2(it is corresponding to 62% volume of air) and the specific refractory power of calculating are 1.18.
embodiment 4
The positively charged SiO that contains 23 % by weight
2aqueous liquid dispersion
By eight hydration zirconyl chloride (the Fluka AG of 6.11g, Buchs, Schweiz), the Wickenol CPS 325 of 4.94g (Locron P, can be from Clariant AG, Muttenz, Switzerland obtains), (Dynasilan 1189 for the normal-butyl aminopropyl trimethyl silane of 4.5g boric acid and 24.8g, 98%, can be from Degussa AG, D ü sseldorf, Germany obtains) in 5 ℃ of deionized waters that are added to successively 729.6g under mechanical stirring.Continuously stirring in during 15 minutes.By the specific surface area of 230g, be 300m
2the pyrolytic silicon dioxide of/g (Cab-O-Sil H5, can be from Cabot Corp., Billerica, USA obtains) at 5 ℃, under violent mechanical stirring, be added in this solution.With rotor-stator high shear mixer, this dispersion liquid is further stirred 10 minutes.During 60 minutes, temperature is increased to 50 ℃, makes afterwards dispersion liquid be cooled to room temperature.Finally, make dispersion liquid by take 45 volume %, be filled with the ball mill Dyno-Mill Multi-Lab (WAB AG Maschinenfabrik) of the zirconium oxide bead that diameter is 0.8-1.0mm with 1.5 liters/h.
In following table, provided the character of this dispersion liquid:
| pH/40℃ | 4.9 |
| At 227s -1The viscosity of/40 ℃ | 32mPas |
| d 50-particle diameter (CPS) | 62nm |
| Polydispersity (CPS) | 1.88 |
| Zeta-potential at pH5 | 38mV |
| Iso-electric point | pH8.7 |
The coating solution that contains the positively charged silicon-dioxide of 14.8 % by weight
Poval PVA235 (the poly (vinyl alcohol) binder that adds 63.4g at 40 ℃ of above-mentioned dispersion liquids to 128.7g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) tensio-active agent Olin G (the Arch Chemicals of 7 % by weight solution, 2.88g, Norwalk, USA) 5.26 % by weight solution and 5.0g deionized water.The pH of this coating solution is 4.9 and it is at 227s
-1viscosity be 70mPas.Ratio between PVA tackiness agent and silicon-dioxide is 15: 100 (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 15.2 μ m.The pore volume of drying layer is 9.2cm
3/ m
2(it is corresponding to 60% volume of air) and the specific refractory power of calculating are 1.19.
embodiment 5
The positively charged SiO that contains 23 % by weight
2aqueous liquid dispersion
By the Rezal67 of 35.9g (pentachloro-hydration zirconium aluminium, Summit Reheis, New-York, USA) (Dynasilan 1189 for the normal-butyl aminopropyl trimethyl silane of 34 % by weight solution, 4.5g boric acid and 24.8g, 98%, can be from Degussa AG, D ü sseldorf, Germany obtains) in 5 ℃ of deionized waters that are added to successively 704.8g under mechanical stirring.Continuously stirring in during 15 minutes.By the specific surface area of 230g, be 300m
2the pyrolytic silicon dioxide of/g (Cab-O-Sil H5, can be from Cabot Corp., Billerica, USA obtains) at 5 ℃, under violent mechanical stirring, be added in this solution.With rotor-stator high shear mixer, this dispersion liquid is further stirred 10 minutes.During 60 minutes, temperature is increased to 50 ℃, makes afterwards dispersion liquid be cooled to room temperature.Finally, make dispersion liquid by take 45 volume %, be filled with the ball mill Dyno-Mill Multi-Lab (WAB AG Maschinenfabrik) of the zirconium oxide bead that diameter is 0.8-1.0mm with 1.5 liters/h.
In following table, provided the character of this dispersion liquid:
| pH/40℃ | 4.7 |
| At 227s -1The viscosity of/40 ℃ | 28mPas |
| d 50-particle diameter (CPS) | 53nm |
| Many 9 divergences (CpS) | 1.52 |
| Zeta-potential at pH5 | 42mV |
| Iso-electric point | pH8.8 |
The coating solution that contains the positively charged silicon-dioxide of 14.8 % by weight
At 40 ℃, to the above-mentioned dispersion liquid of 128.7g, add the Poval PVA235 (poly (vinyl alcohol) binder of 63.4g, Kuraray Europe GmbH, 87-89% degree of hydrolysis, high-polymerization degree) tensio-active agent Olin G (the Arch Chemicals of 7 % by weight solution, 2.88g, Norwalk, USA) 5.26 % by weight solution and 5.0g deionized water.The pH of this coating solution is 4.8 and it is at 227s
-1viscosity be 72mPas.Ratio between PVA tackiness agent and silicon-dioxide is 15: 100 (w/w).
Matrix
Matrix is identical with description in embodiment 1.
Coating in transparent polyester matrix
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 15.4 μ m.The pore volume of drying layer is 9.7cm
3/ m
2(it is corresponding to 63% volume of air) and the specific refractory power of calculating are 1.17.
comparative example 4
The positively charged SiO that contains 20 % by weight
2aqueous liquid dispersion
According to the silica dispersions of embodiment 1 this comparative example of preparation of EP 1 655 348 A1 people such as (, Ilford Imaging Switzerland GmbH) Fuerholz.
The coating solution that contains the positively charged silicon-dioxide of 12 % by weight
Embodiment 1 according to WO 2008/011919 A1 (people such as Beer, Ilford Imaging Switzerland GmbH), utilizes above-mentioned silica dispersions, prepares the coating solution of this comparative example.
Matrix
Matrix is that thickness is that 178 μ m and weight are 248g/m
2transparent polyester carrier (Cronar742, by Dupont Teijin Films, Luxemburg provides).
Coating in transparent polyester matrix
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 14.5 μ m.The pore volume of drying layer is 8.9cm
3/ m
2(it is corresponding to 61% volume of air) and the specific refractory power of calculating are 1.19.
comparative example 5
The positively charged SiO that contains 15 % by weight
2aqueous liquid dispersion
According to the silica dispersions of embodiment 3 these comparative examples of preparation of WO 00/20221 A1 people such as (, Cabot Corp.) Field.
The coating solution that contains the positively charged silicon-dioxide of 12 % by weight
Embodiment 4 according to WO 00/20221 A1, utilizes above-mentioned silica dispersions, prepares the coating solution of this comparative example.
Matrix
Matrix is identical with description in above comparative example 4.
Coating in transparent polyester matrix
At 40 ℃ by 50g/m
2this coating solution be applied on the A3 paper of aforementioned matrix.Afterwards coating matrix is dried to 60 minutes at the temperature of 30 ℃.Cutting A4 paper in the middle of A3 paper, and by its in being placed on the baking oven of 40 ℃ 24 hours to complete process of setting.The thickness of drying layer is 14.5 μ m.The pore volume of drying layer is 7.8cm
3/ m
2(it is corresponding to 57% volume of air) and the specific refractory power of calculating are 1.22.
the discussion of test result
Embodiment 1 and 2 has n
d 20the specific refractory power of <1.2.In addition, embodiment 1 and 2 demonstrates high directly transmission value and low diffuse transmission value.It is excellent that these layers are considered to for most of optical application.
Embodiment 3,4 and 5 has n
d 20the specific refractory power of <1.2.These embodiment demonstrate acceptable direct transmission value and same acceptable diffuse transmission value.These layers are considered to be applicable to for most of optical application.
Comparative example 1 has lower specific refractory power.Yet direct transmission is lower and diffuse transmission is much higher.Because high optical loss, the layer with this character seems not to be suitable for optical application.
Comparative example 2 and 3 demonstrates than the more excellent direct transmission value of comparative example 1 and lower diffuse transmission value.Yet specific refractory power is higher.The layer with this character does not demonstrate the clear superiority for example surpassing, for the conventional layer (, being made by polymkeric substance) of optical application.
Comparative example 4 has the specific refractory power lower than 1.2.Yet diffuse transmission is high and direct transmission is low.The layer with these character is not suitable for optical application.
Comparative example 5 has the specific refractory power higher than 1.2, very high diffuse transmission and low direct transmission.The layer with these character is not suitable for optical application.
Reference numeral
(1) layer structure
(2) stratum basale
(3) PCS layer
(4) silicon oxide particle
(5) extra middle layer (optional)
(6) one or more extra extra plays (optional)
(7) optics
(8) opening
(9) light path
(10) additional layer of outermost (optional)
(11) interior additional layer (optional)
(12) additional layer (optional)
Claims (27)
1. a layer structure (1), described layer structure (1) comprises
(a) stratum basale (2); With
(b) PCS layer (3), described PCS layer (3) is superimposed to described stratum basale (2) at least in part,
Wherein said PCS layer (3) comprises many silicon oxide particles (4),
Wherein said silicon oxide particle (4) has positively charged surface,
The specific refractory power of wherein said PCS layer (3) is less than 1.2.
2. according to claim 1 layer of structure (1), wherein said layer structure (1) forms a freely part for the optics (7) of the group of following composition of choosing: luminescent device, leaded light device, optical transform device, optical recording device, light diffuser part and antireflection device.
3. according to layer structure (1) in any one of the preceding claims wherein, wherein said PCS layer is included in 0.5g/m
2to 25g/m
2amount in scope there is positively charged surperficial silicon oxide particle (4).
4. according in any one of the preceding claims wherein layer structure (1), the mole number based on silicon wherein, in described PCS layer (1), the mol ratio of Al: Si is in the scope of 0.1 to 10 % by mole.
5. according to the layer structure (1) described in any one in claims 1 to 3, the mole number based on silicon wherein, in described PCS layer (3), the mol ratio of Zr: Si is in the scope of 0.05 to 2 % by mole.
6. according to the layer structure (1) described in any one in claim 1 to 5, the mole number based on silicon wherein, in described PCS layer (3), the mol ratio of amino-organosilanes: Si is in the scope of 0.5 to 5.0 % by mole.
7. according in any one of the preceding claims wherein layer structure (1), there is positively charged surperficial silicon oxide particle (4) based on fumed silica described in wherein said PCS layer (3).
8. according in any one of the preceding claims wherein layer structure (1), wherein said have positively charged surperficial silicon oxide particle (4) and have 1 to 200nm median size.
9. according in any one of the preceding claims wherein layer structure (1), the cumulative volume based on described PCS layer (3) wherein, described PCS layer (3) has the pore volume within the scope of 55 to 80 volume %.
10. according to layer structure (1) in any one of the preceding claims wherein, wherein said PCS layer (3) has the thickness within the scope of 1-50 μ m.
11. according in any one of the preceding claims wherein layer structure (1), and wherein said PCS layer (3) is comprised of following ingredients at least:
I) silicon-dioxide of 65-85 % by weight;
Ii) 0.5-10 % by weight is selected from least one compound that comprises aluminium, zirconium or the group of the two;
Iii) amino-organosilanes of 2-10 % by weight;
Iv) tackiness agent of 5-20 % by weight;
V) stiffening agent of 0.5-4 % by weight;
I wherein) to v) part add up to 100%.
12. according in any one of the preceding claims wherein layer structure (1), and wherein said PCS layer has in described layer structure minimum specific refractory power in all layers.
13. according to the layer structure (1) described in any one in claim 1 to 11, wherein said layer structure (1) comprises two above PCS layers (3), and wherein the specific refractory power of these PCS layers (3) is lower than the specific refractory power of any other layer (5,6) in described layer structure (1).
14. according to layer structure (1) in any one of the preceding claims wherein, and the average directly transmissivity of wherein said PCS layer (3) is in 90 to 99.9% scope.
15. according to layer structure (1) in any one of the preceding claims wherein, and the average diffuse transmittance of wherein said PCS layer (3) is less than 4%.
16. according in any one of the preceding claims wherein layer structure (1), has positively charged surperficial silicon oxide particle (4) described in wherein said PCS layer and have at least 0mV, preferably at least 20mV or at least zeta-potential of 30mV.
17. according to layer structure (1) in any one of the preceding claims wherein, described layer structure (1) comprises at least one additional layer (5,6) adjacent with described PCS layer (3), and the specific refractory power height of the refractive index ratio of wherein said at least one additional layer the one PCS layer is 0.2Ge specific refractory power unit at least.
18. 1 kinds for the manufacture of the method with the layer structure (1) of substrate and PCS layer (3), and described method comprises at least following method steps:
(I) provide stratum basale (2);
(II) to described stratum basale (2) stack PCS layer (3),
Wherein said PCS layer (3) comprises many silicon particles (4),
Wherein said silicon oxide particle (4) has positively charged surface;
(III) optionally at least one additional layer (6) is superimposed on described stratum basale (2).
19. method according to claim 18 is wherein carried out step (II) by the following step at least:
I. preparation comprises many have positively charged surperficial silicon oxide particle (4) and the liquid phases of at least one liquid;
Ii. will have 4 to 200g/m
2the described liquid phase of the amount in scope is applied on described stratum basale (2); And afterwards
Iii. be dried the coating forming in step I i, obtain described PCS layer (3).
20. according to the method described in claim 18 or 19, wherein by preparing with following processing fumed silica, has positively charged surperficial silicon oxide particle (4):
I) at least one trivalent aluminum compound; Or
Ii) at least one tetravalence zirconium compounds; Or
Iii) at least one zirconium-aluminium hydration complex compound; Or
Iv) at least one amino-organosilanes; Or
V) reaction product of at least one trivalent aluminum compound and at least one amino-organosilanes; Or
Vi) reaction product of at least one tetravalence zirconium compounds and at least one amino-organosilanes; Or
Vii) reaction product of at least one trivalent aluminum compound and at least one tetravalence zirconium compounds and at least one amino-organosilanes, or
Viii) reaction product of at least one zirconium-aluminium hydration complex compound and amino-organosilanes; Or
Ix) combination of at least two kinds i)-viii).
21. according to claim 18 to the method described in any one in 20, and wherein at least step (II) is carried out with curtain coating method or stepwise coating method.
22. 1 kinds of layer structures (1) that can obtain by the method according to claim 18 to described in any one in 21.
23. according to claim 22 layers of structure (1), wherein said layer structure (1) comprises
(c) stratum basale (2); With
(d) PCS layer (3), described PCS layer (3) is superimposed to described stratum basale (2) at least in part, and described PCS layer comprises many positively charged surperficial silicon oxide particles (4) that have,
The specific refractory power of wherein said PCS layer (3) is less than 1.2.
24. according to the layer structure (1) described in any one in claim 1 to 17 or 22 to 23, the cumulative volume based on described layer wherein, and the pore volume of described PCS layer (3) is in the scope of 55 to 80 volume %.
25. according to the layer structure (1) described in any one in claim 1 to 17 or 22 to 24, and wherein said PCS layer (3) is transparent layer, thermal insulation layer or anti-reflecting layer or the combination of at least two kinds in them.
26. 1 kinds of optics (7), described optics (7) comprises according to the layer structure (1) described in any one in claim 1 to 17 or 22 to 25.
27. are used for optical application according to the layer structure comprising described in any one in claim 1 to 17 or 22 to 25 with positively charged surperficial silicon oxide particle (4), in particular for the purposes of photovoltaic applications.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12000781.0 | 2012-02-07 | ||
| EP12000781.0A EP2626447A1 (en) | 2012-02-07 | 2012-02-07 | Nanoporous layers for optical applications |
| US201261605956P | 2012-03-02 | 2012-03-02 | |
| US61/605,956 | 2012-03-02 | ||
| PCT/EP2013/000363 WO2013117334A1 (en) | 2012-02-07 | 2013-02-07 | Nanoporous layers for optical applications |
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| CN104114745A true CN104114745A (en) | 2014-10-22 |
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|---|---|
| US (1) | US20150331150A1 (en) |
| EP (2) | EP2626447A1 (en) |
| JP (1) | JP2015518172A (en) |
| KR (1) | KR20140132729A (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1099962A1 (en) * | 1999-11-10 | 2001-05-16 | Denglas Technologies, LLC | Niobium oxide-based layers for thin film optical coatings and processes for producing the same |
| CN101035868A (en) * | 2004-10-13 | 2007-09-12 | 依福德成像瑞士有限公司 | Recording sheet for ink jet printing |
| CN101501533A (en) * | 2006-07-28 | 2009-08-05 | 依福德成像瑞士有限公司 | Flexible materials for optical applications |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3903258A (en) | 1973-08-06 | 1975-09-02 | Gillette Co | Zirconium aluminum complexes and method of making the same |
| US5179220A (en) | 1991-07-01 | 1993-01-12 | Somerville Technology Group, Inc. | Non-aqueous solutions of aluminum and aluminum-zirconium compounds |
| US6420039B1 (en) * | 1998-10-02 | 2002-07-16 | Cabot Corporation | Recording medium |
| JP2009175673A (en) * | 2007-12-27 | 2009-08-06 | Hitachi Chem Co Ltd | Coating liquid set for low refractive index film |
| EP2112204A1 (en) * | 2008-03-01 | 2009-10-28 | ILFORD Imaging Switzerland GmbH | Recording sheet for ink jet printing |
| EP2164302A1 (en) * | 2008-09-12 | 2010-03-17 | Ilford Imaging Switzerland Gmbh | Optical element and method for its production |
-
2012
- 2012-02-07 EP EP12000781.0A patent/EP2626447A1/en not_active Withdrawn
-
2013
- 2013-02-07 CN CN201380008510.7A patent/CN104114745A/en active Pending
- 2013-02-07 US US14/377,279 patent/US20150331150A1/en not_active Abandoned
- 2013-02-07 EP EP13703733.9A patent/EP2941494A1/en not_active Withdrawn
- 2013-02-07 KR KR1020147025255A patent/KR20140132729A/en not_active Application Discontinuation
- 2013-02-07 JP JP2014555973A patent/JP2015518172A/en active Pending
- 2013-02-07 WO PCT/EP2013/000363 patent/WO2013117334A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1099962A1 (en) * | 1999-11-10 | 2001-05-16 | Denglas Technologies, LLC | Niobium oxide-based layers for thin film optical coatings and processes for producing the same |
| CN101035868A (en) * | 2004-10-13 | 2007-09-12 | 依福德成像瑞士有限公司 | Recording sheet for ink jet printing |
| CN101501533A (en) * | 2006-07-28 | 2009-08-05 | 依福德成像瑞士有限公司 | Flexible materials for optical applications |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105974664A (en) * | 2016-06-21 | 2016-09-28 | 青岛海信电器股份有限公司 | Backlight module, display device and manufacturing method of backlight module |
| CN105974664B (en) * | 2016-06-21 | 2019-12-31 | 青岛海信电器股份有限公司 | Backlight module, display device and manufacturing method of backlight module |
| CN110023423A (en) * | 2016-11-22 | 2019-07-16 | 巴斯夫涂料有限公司 | Optical coating with low-refraction |
| CN108445567A (en) * | 2018-03-30 | 2018-08-24 | 苏州沛斯仁光电科技有限公司 | A kind of high-reflecting film and preparation method of high damage threshold |
| US10734592B2 (en) | 2018-05-28 | 2020-08-04 | Hefei Boe Optoelectronics Technology Co., Ltd. | Method for manufacturing thermal insulation film, thermal insulation structure, and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2626447A1 (en) | 2013-08-14 |
| JP2015518172A (en) | 2015-06-25 |
| US20150331150A1 (en) | 2015-11-19 |
| WO2013117334A1 (en) | 2013-08-15 |
| EP2941494A1 (en) | 2015-11-11 |
| KR20140132729A (en) | 2014-11-18 |
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